Quaternary ammonium salts



Patented June 4,1940- UNITED STATES PATENT OFFICE QUATERNARY AMMONIUM SALTS- No Drawing; Application February 9,1937, Se-

rial No. 124,922. 1936 14 Claims.

This invention relates to the manufacture of new quaternary ammonium salts.

This invention has as an object to devise a method of manufacturing new aromatic quaternary ammonium compounds. A further object is to produce new aromatic quaternary ammonium compounds. A further object is to produce new reagents from which the new quaternary ammonium compounds can be prepared. Further objects will appear hereafter.

These objects are achieved by the following invention. We have found that we can manufacture new quaternary ammonium salts by interacting a dialkylaminobenzoate of the general 15 formula ROOC-Ar-N X go where Ar represents a residue of the benzene series, X and X each represent a lower alkyl (methyl to butyl) radicle and R represents a long chain aliphatic hydrocarbon radicle having 10 to carbon atoms, with an alkyl ester of an inorganic acid or of an organic sulfonic acid,

In manufacturing the new quaternary ammonium salts of the present invention, interaction is conveniently brought about by heating the defined reagents together at moderately raised so temperatures, for example, 90-100 C. In most cases the reaction mixture is fluid at such temperatures and the use of an inert liquid diluent is not necessary but such a diluent, for example, a hydrocarbon such as toluene, may be present if 85 desired.

The reagents of the general formula hereinbefore given are, as will be seen, esters of aliphatic alcohols having 10-20 carbon atoms. These alcohols, which are used as starting ma- 0 terials in the making of the intermediates to be used according to the invention, comprise dodecyl alcohol, otherwise known as dodecanol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, all of which are saturated. Hexadecyl alcohol is the main or sole component of the alcohols obtained by the saponification of spermaceti. If the alcohol obtained by the saponification of spermaceti is regarded as hexadecyl alcohol, its purity will depend upon the purity of the spermaceti which has been saponi- In Great Britain February 12,

I fled. With low grade spermacetiv the alcohol obtained is a mixture which may contain also oleyl alcohol. When the term cetyl alcohol is used in this specification, it will be understood that it does not necessarily refer to pure cetyl alcohol.

The reagents of the given general formula which are new compounds are readily prepared by applying the methods hereinafter indicated. The new dialkylaminobenzoates disclosed herein are claimed in a division of this application, Serial No. 219,096 filed July 13, 1938.

The new quaternary ammonium salts manu-' factured according to the present invention are solids which dissolve in water to give foaming solutions. On warming these aqueous solutions with alkali the foaming power disappears and the solutions become turbid or opalescent. The salts are unstable to alkali and slowly decompose under the conditions of alkalinity and temperature usually prevailing in the application of a vat dyestufl.

The invention .is illustrated but not limited by the following examples, in which the parts are by weight.

Example 1 The cetyl p-dimethylaminobenzoate used in the above example may bemade by reacting 18.4 parts of p-dimethylaminobenzoyl chloride with 25 parts of cetyl alcohol in the presence of parts of dimethylaniline at C. for 18 hours and then removing the dimethylaniline from the reaction product by washing with dilute hydrochloric acid. when crystallized from methanol, cetyl p-dimethylaminobenzoate is' a crystalline solid m. p. 86-67 C. and has the formula Example 2 The dodecyl p-dimethylaminobenzoate used in the above example is a new compound and was prepared as follows: A solution of p-dimethyl- CHI amino benzoyl chloride in dimethylaniline was prepared by passing phosgene into 9'16 parts of dimethylaniline at below 20 C. until the increase in weight indicated that 200 parts of phosgene had been taken up. After standing for 18 hours, during which time the temperature of the solution rose to 80 C. and then slowly fell to room temperature, 488 parts of dimethylaniline and 221 parts of dodecyl alcohol were added and the mixture heated at 100 C. for 4 hours. The reaction mixture was then poured into 5,000 parts of aqueous 2N hydrochloric acid and the whole was then cooled to atmospheric temperature and extracted with ether. The ether extract was washed with water, then with dilute aqueous sodium carbonate to remove any traces of excess hydrochloric acid, finally dried with anhydrous magnesium sulfate, and the ether evaporated off- The oily residue was purified by crystallization from methyl alcohol whereby dodecyl p-dimethylaminobenzoate was obtained in the form of colorless crystals, m. 9. 50 0. having the formula Example 3 O W a (I) 0,115 CHr-O--S=O CHI ' apoaeea Cetyl p-diethylaminobenzoate, m. p. 4648 C. is prepared from diethylaniline, phosgene and cetyl alcohol in a similar manner to that already described for the preparation or dodecylp-dimethylaminobenzoate and has the formula Example 4 40 parts of oleyl p-dimethylaminobenzoate (golden yellow oil, b. p. 240-275 C./3 mm., prepared by reacting technical oleyl alcohol with pdimcthylaminobenzoyl chloride in dimethylaniline and having the formula where 01 stands for the radicle of oleyl alcohol) and 13.0 parts of dimethyl sulfate are heated together and the product isolated as described in Example 2. Oleyl p-dimethylaminobenzoate methosulfate is thus obtained as a pale yellow semi-crystalline mass which dissolvesin hot water to give foaming solutions having the formula CH3 o I on! Ol-O-G N where 0] stands for the radicle of o leyi alcohol.

Example 5 CH1 0 I 01H: 0 H 0 PJGN l6 3 I 01H Clive- 5:0

The cetyl p-diethylamino-o-toluate used in the above example is prepared by first interacting phosgene with an excess of 3-diethylaminotoluene and then reacting the product with cetyl alcohol. It has the formula C H: O I Call:

ll C cHar-O-C 'N\ CaHs Example 6 Equal weights of cetyl p-dimethylaminobenzoate and diethyl sulfate are heated together for 6 hours at 90 C. in a closed vessel. The watersoluble reaction product is purified by crystallisation from acetone whereby cetyl p-dimethylmethosulfate, m. p.

aminobenzoate ethosulfate m. p. HP-80 C. is obtained and has the formula CIHI 0 I OH: II CuBlt-O-C N C H: CsHnO-S-O Example 7 CHI Cetyl p-methylbutylaminobenzoate is obtained by reacting phosgene with an excess of N-methylbutylaniline and then reacting the sO-obtained N-methylbutylaniline solution of p-N-methylbutylaminobenzoyl chloride with cetyl alcohol. It has the formula Example 8 CHI CH: O I OH: II C1aHn--OC N\ O CH:

The new quaternary ammonium compounds disclosed herein are valuable assistants for use in connection with the application of vat dyestuffs to cellulosic textile materials. Their use for this purpose is illustrated by Examples 2, 3, and 11 to 17 of applicants British Patent 470,346, which correspond with examples which have been. deleted from the present application.

Further examples of suitable alkyl esters of inorganic acids and organic sulfonic acids are methyl bromide, methyl iodide, ethyl bromide, diethyl sulfate, isopropyl bromide, butyl chloride, amyl chloride, allyl bromide, ethyl p-toluenesulfonate methyl benzene sulfonate, etc.

The invention is not limited to the use of esters of the alcohols mentioned above altho for economic reasons we prefer to use alcohols with an even number of carbon atoms. Dodecyl and' tetradecyl alcohols are obtainable by reduction of the fatty acids obtained from coconut oil and palm oil. Other alcohols, e. g. olein" or oleyl alcohol (better to be known as octadecenol) are likewise obtainable by reduction of the fatty acids of natural fats and oils (see here, for instance. Bouveault andBlanc, Bull. Soc. Chim., Series 3, vol. 31, page 1, pages 674 and 1210). The invention contemplates the use of the said esters of any of these alcohols, whether in the pure state or as obtained as mixtures from the fatty acids of natural fats and oils. Convenient alternative description of .the said esters is accordingly that they are those of primary alcohols resulting from the reduction of the fatty acid radicles of natural fats and oils or from the saponification of waxes.

This invention is a valuable advance in the art as it extends the range of compounds which can be used with vat dyestufis to build up level shades and discloses new compounds more effective than those known in the prior art.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. New quaternary ammonium salts having the general formula:

and X each represent a lower alkyl group containing from 1 to 4 carbon atoms, and Y represents the anion of an acid selected from the class consisting of inorganic acids and organic sulfonic acids.

2. A process of making the quaternary ammonium salts defined in claim 1 which comprises reacting a compound having the general formula:

wherein R represents a long chain aliphatic hydrocarbon group containing from 10 to 20 carbon atoms, Ar denotes an aromatic radical of the benzene series selected from the class consisting of phenylene and methylphenylene radicals, and X and X each represent a lower alkyl group containing from 1 to 4 carbon atoms, with an alkyl ester of an acid selected from the class consisting of inorganic acids and organic sulfonic acids.

3. New quaternary ammonium salts having the general formula:

OSOaAlk wherein R represents a long chain aliphatic hydrocarbon group containing from 10 to 20 carbon atoms and Alk denotes in each instance an alkyl group containing from 1 to 2 carbon atoms.

4. A process of making the quaternary ammonium salts defined in claim 3 which comprises reacting a dialkylaminobenzoate havlng the general formula:

Q ROOC- N I on, Rooo-ON V C a OSOtCHa wherein R represents a straight chain aliphatic hydrocarbon group containing from 12 to 18 carbon atoms. I

6. A process of making the quaternary ammonium salts defined in claim 5 which comprises heating a dimethylaminobenzoate having the general formula:

on. ROOC-O-N/ wherein R represents a straight chain aliphatic hydrocarbon group containing from 12 to 18 carbon atoms with dimethyl sulfate until a sample of the reaction mixture is soluble in water.

I. Cetyl p-dimethylaminobenzoate methosulfate which has the formula:

8. A process of making cetyl p-dimethylaminobenzoate methosulfate which comprises heating cetyl p-dimethylaminobenzoate with neutral dimethyl sulfate in a closed vessel at -95 C. until a sample of the reaction mixture is completely soluble in water.

9. Cetyl p-diethylaminobenzoate methosulfate which has the formula:

10. A process of making cetyl p-diethylaminobenzoate methosulfate which comprises heating cetyl p-diethylaminobenzoate with dimethyl sulfate at about C. until a sample of the re action mixture is completely soluble in water.

11. Oieyl p-dimethylaminobenzoate methosulfate which has the formula:

O I O 01-0--O-I/ wherein ()1 stands for the hydrocarbon radical of oleyl alcohol.

12. A process of making oleyl p-dimethylaminobenzoate methosulfate which comprises heating oleyl p-dimethylaminobenzoate with dimethyl sulfate.

13. New quaternary ammonium salts having the general formula:

ROOCOE LUKD SOgCH;

wherein R represents a straight chain aliphatic hydrocarbon group containing from 16 to 18 carbon atoms and Alk denotes in each instance an alkyl group containing from 1 to 2 carbon atoms.

14. A process of making the quaternary ammonium salts defined in claim 13 which comprises heating a dialkylaminobenzoate having the general formula:

x ROOCO-N wherein R represents a straight chain aliphatic hydrocarbon group containing from 16 to 18 car bon atoms, and X and X each represent an alkyl group containing from 1 to 2 carbon atoms with dimethyl sulfate.

HENRY ALFRED PIGGO'IT. CLARENCE SYDNEY WOOLVIN. 

